Resin and process for its manufacture



Patented Oct. 20, 1 953 RESIN AND PROCESS FOR rrs MANUFACTURE Herman S.Bloch, Chicago, Ill., assignor to Universal Oil Products Company,Chicago, 111., a

corporation of Delaware No Drawing. Application June 14, 1951, SerialNo. 231,667

13 Claims. 1

This application is a continuatiOn-in-part of my copending applicationSerial Number 782,022, filed October 24, 1947, now patent No. 2,558,812,which in turn is a continuation-in-part of my application Serial Number534,155, filed May 4, 1944, and now abandoned.

'This invention relates to the preparation of high molecular weightcondensation products and resins which are useful in the manufacture ofother resinous materials that may be used as coating compositions, maybe molded into articles of manufacture or may be employed as binders forthe production of molding cores and the like.

An object of this invention is to prepare a resin with high softeningpoint, good strength, and

hardness, and having improved adhesion to surfaces of wood and metals.

One embodiment of this invention relates to a process for producing asynthetic resin which comprises reacting in the presence of a strongmineral acid catalyst a polyenic hydrocarbon, a phenol having at least 2substitutable nuclear hydrogen atoms, and an aromatic hydrocarbon havingat least 2 replaceable nuclear hydrogen atoms and alkyl groups of notmore than 2 carbon atoms to form an organic condensation product andfurther reacting said condensation product with a carbonyl compoundselected from the group consisting'of an aldehyde and a ketone to form aresin.

Another embodiment of this invention relates to a process for producinga synthetic resin which comprises reacting in the presence of a strongmineral acid catalyst a polyenic hydrocarbon, 2, phenol having at least2 substitutable nuclear hydrogen atoms, and an alkyl aromatichydrocarbon which has at least 2 replaceable nuclear hydrogen atoms andin which said alkyl group contains not more than 2 carbon atoms to forman organic condensation'product, separating said organic condensationproduct, unconverted reactants and catalyst from the resultant reactionmixture, reacting said condensation product in the presence of acatalyst with a carbonyl compound selected from the-group consisting ofan aldehyde and'a ketone to form a resin, and recovering said resin fromthe reaction products.

A "further embodiment of this invention re lates to a process formanufacturing a resin which comprises reacting in the presence of astrong mineral acid catalyst .a major proportion of a polyenichydrocarbon and minor molecular proportions of a phenol having at leasttwo nuclear hydrogen atoms and an alkyl aromatic hydrocarbon having atleast 2 nuclear hydrogen atoms and an alkyl group of not more than 2carbon atoms, further reacting the resultant reaction mixture with acarbonyl compound selected from the members of the group consisting ofan aldehyde and a ketone, stopping the reaction by treating the reactionmixture with a member of the group consisting of water and an aqueousalkaline solution and separating the resultant resinous product fromunconverted organic materials and aqueous solution.

An additional embodiment of this invention relates to a process for theproduction of a resinous product which comprises reacting a mixture ofaryla'lkyl phenols and arylalkenyl phenols with a carbonyl compoundselected from the group consisting of the aldehydes and ketones in thepresence of an acidic condensation catalyst at a temperature of fromabout 25 C. to about 200 C. and in the molar ratio of said carbonylcompound to said phenols of from about 0.5 to about 2, said phenolsbeing the condensation product of a hydroxy aromatic hydrocarbon havingat least 2 substitutable nuclear hydrogen atoms with both a polyenichydrocarbon and an aromatic hydrocarbon having at least 2 replaceablenuclear hydrogenatoms and all y1 groups of not more than 2 carbon atoms.

The incorporation of a phenolic material in the resins of my inventionresults in an improvement over the analogous hydrocarbon resins withrespect to solubility in oxygenated solvents, such as esters and ethers,as well as an increase in softening point, hardness, and strength of thefinished resins. When employed in coating compositions thephenol-containing resins show improved adhesion to metals and woods andgenerally have more satisfactory durability than the purely hydrocarbonresins.

Broadly, my invention comprises preparing a resinous material havingimproved adhesive and coating qualities by reacting an aromatichydrocarbon and a phenolic material with a polyene in the presence of anacidic catalyst, and further reacting the resultant reaction mixturewith a carbonyl compound selected from the group consisting of fanaldehyde and ketone.

The polyenic "hydrocarbons preferred as starting materials in thisprocess have two conjugated double bonds per molecule and includebutadiene-.1,3; isoprene; piperylene; cyclopentadiene; cyclohexadieneand other cyclic hydrocarbons having at least two double bonds per.molecule. Such cyclic hydrocarbons include polycyclic unsaturatedhydrocarbons shaving conjugated and also non-conjugated unsaturation andformed under the influence of strong acidic catalysts as sulfuric acid,hydrogen fluoride, etc. from aliphatic hydrocarbons and particularlyfrom olefins.

The alkyl aromatic hydrocarbons used in this process should have atleast two nuclear hydrogen atoms which may be replaced by reaction withpolyolefins and phenols. These alkyl aromatic hydrocarbons includetoluene, ethylbenzene, and other alkyl aromatic hydrocarbons havingalkyl groups of not more than two carbon atoms. Alkylated naphthaleneand other alkylated polycyclic hydrocarbons are also useful in theprocess but benzene, naphthalene and other polynuclear aromatics freefrom alkyl substituents generally yield resins which have low solubilityin most organic solvents and accordingly, are less desirable in thisprocess.

Pure alkyl aromatic hydrocarbons may be used 52 or a fraction containingalkyl aromatic hydrocarbons and substantially saturated hydrocarbons maybe employed. Such hydrocarbon fractions containing alkyl aromatichydrocarbons may boil in the range of gasoline, kerosene, or evenheavier fractions.

The phenolic reactants of this process which include phenol,mono-alkylphenols, polyalkylphenols, cyclo-alkylphenols, arylphenols,and

polynuclearphenols such as naphthols and tetrahydronaphthols have atleast two and better 3 or 4 hydrogen atoms combined with carbon atoms ofthe phenolic ring in order to produce a high melting resin. A phenolhaving 3 or 4 readily replaceable nuclear hydrogen atoms is not onlyable to react with diolefinic and aromatic hydrocarbons to form longchain resin molecules, but this resin may be reacted further withaldehydes and ketones as hereinafter set forth.

The aromatic hydrocarbon fraction charged to the process should containat least of usable alkyl aromatic hydrocarbons and should besubstantially free from non-alkylated aromatics. The lower limit of theproportion of phenols charged should be at least about 10 mole per centof the total of alkyl aromatic hydrocarbons and phenols. This lowerlimit of phenol proportion is essential so that the finished resin(which may vary in molecular weight from about 500 to about 1500) mayhave incorporated therein an average of at least one phenolic nucleusper molecule. The total amountof phenolic material present in thereaction mixture should be not more than about mole per cent of thetotal of the alkyl aromatic hydrocarbons plus phenols contained in themixture. In forming the resin of this process, the preferred molecularratio of polyene to the total of alkyl aromatic hydrocarbons plusphenols is generally about one if dienes are used or this ratio is lessthan one if the polyenes are more unsaturated than the dienes. If ahard-finish resin is desired, a little more than a mole, i. e., about1.5 moles per mole of aromatic are used. If, however, it is desired toproduce a soft resinoid which is to be further reacted, as for example,with formaldehyde, the mole to mole ratio is preferred. By reacting theresinoid with formaldehyde or other aldehydes or ketones, harderthermosetting resins may be prepared.

Aldehydes and ketones suitable for use in this process may be aliphaticor cyclic and of either saturated or unsaturated structure. Also thecyclic carbonyl compounds may be either cycloparafiinic or aromatic.Suitable ketones include such saturated members as acetone, methylethylketone, diethyl ketone, etc. cyclic saturated ketones, such asmethylcyclohexyl ketone; cyclic members wherein the carbonyl group ispart of the ring, such as eyclohexanone; unsaturated ketones, such asvinyl methylketone, ethylideneacetone, mesityl oxide, phorone,isophorone, etc.; aryl ketones, such as acetophenone, butyrophenone,benzophenone, etc.; alkenyl arylketones, such as propenyl phenylketones; polyketones, such as diacetyl or benzil and homologs of theabove classes. Typical aldehydes of the corresponding classes enumeratedabove include such compounds as formaldehyde and acetaldehyde of thesaturated aliphatic series, crotonaldehyde or acrolein of theunsaturated aliphatic series, benzaldehyde or cinnamaldehyde of thearylal'dehydes, and heterccyclic aldehydes such as furfural. Thepolymers of formaldehyde such as trioxymethylene are particularly usefulsince the latter are liquid at elevated temperatures and depolymerizeduring the reaction to yield the highly active carbonyl compound,formaldehyde. The aldehydes and ketones may also be employed inadmixture with each other or with members of the same group. Thecarbonyl reactant may also contain diverse radicals other than thecarbonyl group attached to other carbon atoms in the structure of thecompound than the carbonyl carbon atoms, thereby introducing variousmodifications in the properties of the ultimate resinous product. Suchother radicals may be one or more or" the following group: halogen,nitro, amino, alkoxy, acyloxy, carboxy, carboxamide, or sulfonic acidradicals, which, although they do not enter into the condensationreaction directly with the hydroxy aromatic compound (i. e., are notphenol-reactive) nevertheless affect the melting point, solubility andother characteristics of the resin. In general, when utilizing anunsaturated carbonyl compound, as for example, a ketone or aldehydewherein the carbonyl group is attached to an alkenyl residue, theproducts tend to have somewhat different properties than resins preparedfrom the corresponding saturated carbonyl reactants containing the samenumber of carbon atoms. As a rule, the products derived from theunsaturated series of reactants tend to have higher melting points due,it is believed, to incidental polymerization effects obtained betweenthe double bonds of said reactants.

In the first step of this process the reactants are charged in theproportions of from about 5 to about 25 mols of phenols from about 25 toabout 45 mols of alkyl aromatic hydrocarbons and from about 50 to about75 mols of polyenes, the latter preferably conjugated alkadienes.Accordingly, a typical reaction mixture contains from 10 to 50 molecularproportions of a phenol or phenol mixture, from to 50 molecularproportions of xylenes, ethylbenzene or other suitable aromatichydrocarbon or aromatic hydrocarbon mixture, and from to molecularproportions of polyenic hydrocarbon such as butadiene-l .,3. If lessdienic or other polyenic hydrocarbon is present in the reaction mixturethan that needed to react with the aromatic hydrocarbons as well as thephenols the resultant resin will contain substantial amounts of aphenol-polyene condensation product which may be liquid. When thespecified proportions of the three reactants are present, much betteryields of a hard resin are formed by the interaction of all three ofthese resin components, namely phenol, alkyl aromatic hydrocarbon andpolyene. It appears that the phenols react more rapidly than the alkylestates Strong mineral acids which are suitable as catv alysts for thefirst step of this process comprise sulfuric acid, phosphoric acid andhydrofluoric acid. These different catalysts are not necess'arilyemployed at the same conditions of operation nor are equivalent resultsobtained in their presence. The sulfuric acid catalyst preferablycontains at least 90% by weight of I-IiSCh, the remainder being water,but the catalyst should contain 95% or more of H280; in order to promotehigh reaction efliciency. Hydrogen fluoride catalyst which is alsoreferred to as hymn-11mm acid should also contain at least 907 by lot ofl-IE and preferably more than 95% by weight of HF. Phosphoric acidscontaining about 90% by weight of HsPO4 may also be used, but a higheryield of resin is obtained when employing a ilesphoric acid catalyst ofhigher concentration.

In carrying out the first step process of this invention, the mixture ofphenol and the aromatic hydrocarbons or the hydrocarbon fractioncontaining aromatics is commingled with a stoichiometric equivalent orexcess of polyenic hydrocar bon and heated in the presence of thecatalyst at a temperature usually below about 150 but generally in therange of to 50 C. The reaction mixture is then treated with water or anaqueous solution of an alkali for the purpose of inactivating thecatalyst, stopping the reaction, and decomposing the complexes ofcatalyst with organic material. When using sulfuric acid eatalyst, arefluxing treatment of theorganic aque= ous two phase system decomposesthe emulsifying sulfonic acids and assists in the separation of theresinous product from the uncondensed jorganic material and the aqueousphase. The last step can be done by steam-distilling the two phasesystem and subsequently separating the resinous residue from the aqueousphase, or by first separating the aqueous phase and thenvacuum-distilling or steam-distilling the organic phase; the exact orderor manner of procedure is generally unimportant. After the unreactedmaterial and Water are removed from the plastic residue as by heating at90 to 200 C. and the plastic residue is permitted to cool, it setsquickly to form a clear, pale resin having good solubil ities inaromatic hydrocarbons, chlorinated ray drocarbons, and higher members ofthe series of lacquer solvents of the ester, ketone, glycol-ester, andglycol-ester types. A

The separation of olefin polymers and unreacted material such as excesspolyene, phenol or I non-aromatic hydrocarbons (in cases wherein naphthafractions are employed instead cf pure hydrocarbons) is preferablyeffected by steam distillation rather than by ordinary distillationunless the latter is carried out at subatmospheric pressure.Distillation at atmospheric pressure causes darkening of the resinousproduct.

When anhydrous hydrogen fluoride is em v ployed as the catalyst for thereaction, the reaction products may be decomposed by heat and thesubstantially anhydrous hydroge'n fluoride recovered for further use.The remaining ma terial is treated as before to remove unreactedcomponents and olefin polymers and the plastic residue freed from waterto yield the desired resin.

In an alternative method of procedure, the phenol is added to thereaction mixture after partial condensation has been effected between 6the aromatic hydrocarbon and the polyenic inatei'ial; Less Catalyst isneeded when renewin this method of operation but greater care isrequired to ifisiiie a homogeneous product having satisfactoryproperties.

The composition and properties of the resin prepared according to themethod herein'abOVe set forth may be varied if, instead of or togetherwith the phenol, other substituted aromatic compounds are employed.These compounds include aromatic amines or simple derivatives thereof,

aromatic carboxylic acids or their simple deriva tives, aromaticalcohols or derivatives thereof, aromatic aldehydes or their acetals,aromatic nitro or nitroso compounds or aromatic 'sulfonic acids or theirsimple derivatives.

The resinous condensation product formed as hereinabove set forth byreacting a phenol, an alkyl aromatic hydrocarbon and a polyenichydrocarbon in the presence of a strong mineral acid catalyst may beregarded as a mixture of arylalkyl phenols and arylalkenyl phenolsformed by the condensation of an aromatic hydrocarbon and a phenol witha diolefin, a diolefin polymer or other polyolefin to form a highmolecular weight condensation product. Such a mixture of arylalkylphenols and arylalkenyl phenols is then reacted further with a carbonylcompound selected from the group consisting of an aldehyde and a ketoneto produce a higher molecular weight condensation product which isuseful as a thermosetting resin and as a surface coating material. Thecondensation of a carbonyl compound selected from the group consistingof an aldehyde and a ketone with the reaction product obtained in thefirst step of this process is preferably carried out in the presence ofa catalyst selected from the group consisting of acid-acting substancesand basic substances. The acidacting substances are selected from eitherthe organic or mineral acids, including such acids as acetic,chloroacetic, citric and oxalic acids, 'various sulfonic acids, such asethanesulfonic acid, etc. of the former class and hydrochloric,sulfuric, phosphoric,etc. acids of the mineral acid class of catalysts.The catalyst is introducedinto the reaction mixture in suflicientquantity to result in a slightly acidic reaction mixture, generally inamounts of from about 0.1 to about 10 weight per cent of the reactionmixture. When utilizing mineral acid catalysts, the quantity of catalystis generally less than about 5%, whereas organic acids may be present inamounts up to about 10% of the reaction mixture. The catalyst may besubsequenuy removed from the resinous roduct by contacting the resinousreaction mixture with a solvent which has a selective solubility for thecatalyst, such as water containing a base or alkali, or the resin may bedissolved away from the catalyst, as for example, by contacting theresin containing the catalyst with a hydrocarbon such as benzene whichdissolves the resin but not the catalyst.

The condensation reaction may be conducted in the presence of a solventfor the reactants, the solvent tending to modify the rate of reactionand the character of the products obtained there'- from. In general, thealiphatic alcohols such as butyl alcohol, ethers, such as diethylether,esters, such as ethylacetate, halogenated hydrocarbons, such as ethylenedichloride or trichloroethylene, and hydrocarbon solvents (particularlythe aromatics such as benzene, toluene, etc.) provide suitable solventsor diluents in which to conduct the reaction. The solvent may be addedfor the specific purpose of controlling the rate of reaction, as forexample, where a solvent is chosen which vaporizes at the reactiontemperature and thus maintains its temperature at the boiling point ofthe solvent. The solvent may also form an azeotrope with the by-productwater formed in the reaction and thus provide an effective means forremoving the latter undesirable product from the reaction mixture.

The resin-forming reaction of the present process may be eifected attemperatures of from about to about 200 C. and preferably from about toabout 125 C. and at pressures sufficient to maintain the reactants insubstantially liquid phase. The proportion of carbonyl compound to thecondensation product formed from a phenol, an aromatic hydrocarbon and apolyene utilized in the reaction mixture may vary from about 0.5 toabout 2 molecular proportions thereof. It is generally preferred tomaintain the molecular ratio of carbonyl compound to the previouslyformed condensation product within the range of from about 0.7 to about1.2 as the resinous product obtained thereby generally possesses moredesirable characteristics. In general, lowering said above ratio resultsin the production of a soft resinous material whereas increasing theratio tends to produce resins of hard, brittle characteristics. Withinthe range specified, the resins may vary from soft resins or fluidresinoids to hard, tough elastic products, depending upon the degree ofcondensation desired for the particular use intended. In either case,the resins possess the ability to condense and polymerize further by theaction of heat and pressure with or without polymerization catalystssuch as peroxides, organic acids, or acidacting salts like zincchloride.

The residual unsaturation contained in the resinous products is believedto account for the ability of the resins to undergo furtherpolymerization under the influence of heat and pressure, etc. Forsimilar reasons, the products may be vulcanized in the presence ofsulfur when subject to heat and pressure in the presence of suitableaccelerators. Because of the unusual combination of properties found inthe present resinous products, they should find wide use as moldingmaterials, coatings, rubber additives, adhesives and impregnants forcloth, wood and paper,

as for example in the manufacture of laminated products. The quality ofthe resins may be varied within wide limits to secure products of almostany specified properties varying in hardness, solubility, setting time,etc. by the regulation of the reactant ratios in the condensationreaction, the type and boiling rmge of the phenols, aromatichydrocarbons and polyolefinic hydrocarbons, the type of carbonylcompound, the nature and amount of catalyst used, the degree ofreaction, etc. Further variations may be obtained by blending theresultant resinous products with resins of other types, especiallyurea-aldehyde, melamine-aldehyde, and other phenolic resins.

As hereinabove set forth the second step of the process, that is thefurther reaction of a carbonyl compound with the condensation product ofphenol, an aromatic hydrocarbon and a polyenic hydrocarbon may becarried out in the presence of a basic catalyst in a manner similar tothat employed when utilizing either an organic acid or mineral acidcatalyst. The basic catalysts employed in this step of the processcomprise organic and inorganic bases and particularly basic nitrogencompounds. Such basic nitrogen compounds include ammonia, an amine, ahetero- Example I 159.1 grams of xylenes and 47.05 grams of phenol werecombined and introduced to a reactor equipped with a stirring device.The reactor was chilled and 102 grams of 96% sulfuric acid was added.120 grams of butadiene was introduced slowly to the reaction mixturewhich was maintained at a temperature of 5 to 10 C. for six hours. Waterwas then added to the reaction mixture which was then heated underreflux for one hour (during which sulfonic acids were decomposed), andthe entire mixture was then steam-distilled to remove any unreactedxylenes and phenol. The steam-distillate was a water-white aromaticliquid containing 82% of xylenes. The residue from thesteam-distillation after being freed from water by vacuum-distill tionwas a resinous solid with a Softening point (ball and ring) of 131 F.The resinous solids so obtained weighed 225.5 grams.

45.4 grams of the condensation product formed from the abovecondensation of xylenes, phenol, and butadiene dissolved in ethylenedichloride employed as solvent was mixed with 3.5 grams oftrioxymethylene (an amount sufilcient to provide slightly over a molarequivalent of formaldehyde) in the reaction mixture. To this mix ture 1%by weight of oxalic acid was added as catalyst and the resultant mixturewas heated to a temperature of approximately 55 C. for a time of 2hours. A viscous reaction product soon formed which on further reactionat the indicated conditions produced a flexible but tough and hardresinous mass. This material could be subjected to vulcanization andconsequent further hardening by incorporating from 1 to 10% by weight ofsulfur therein and heating under pressure at a temperature of 150 C. for1 hours.

Example II A mixture of 159.1 grams of xylenes, 47.05 of phenol, and 120grams of butadiene was reacted in the presence of 93 grams of phosphoricacid HsPOi and 10% water). At temperatures up to 50 C., reaction wascomparatively slow and yields were quite small, but at highertemperatures the reaction occurs more rapidly and better yields wereobtained. The products of reaction were treated as in Example I torecover a resinous product similar to that formed when sulfuric acid wasused as the catalyst. 45.4 grams of the resinous product obtained inthis run and 15.2 grams of isophorone were heated at a temperature of C.for 4 hours in the presence of 0.2% by weight of concentrated phosphoricacid to form a hard resinous mass which was then washed with water andcaustic to remove phosphoric acid catalyst. The water washed and causticwashed resinous reaction product was then dried to give a material foundsuitable for molding into plates, bars and other objects.

Example III In this run, 201 grams of hydrogen fluoride was used as thecatalyst for the reaction of a mixture of 212 grams xylenes, 63 gramsphenol and 149 grams of butadiene; the latter was added gradually over aperiod of two hours. The reaction was conducted at a temperature of fromExample IV 68.1 grams of the xylene-phenol-butadiene resinoid recoveredas an intermediate in Example I was refluxed for two hours with 0.25mols of formalin (added as 35% aqueous formaldehyde) in the presence of0.005 mol of sodium hydroxide. The product gradually hardened duringthis period, and at the end of this period formed a firm solid which wasrendered quite hard by curing at 150 C. A similar product was ob tainedwhen an equivalent amount of ammonia was used as catalyst instead ofsodium hydroxide, but six hours were required for the condensation.

I claimas my invention:

1. A process for producing a synthetic resin which comprises reacting acarbonyl compound selected from the group consisting of aldehydes andketones with the condensation product of from about to about 25 mols ofa phenol having at least two nuclear hydrogen atoms, from about 25 toabout 45 mols of an aromatic hydrocarbon having at least two nuclearhydrogen atoms and an alkyl group of not more than two carbon atoms, andfrom about 50 to about 75 mols of a conjugated aliphatic dienehydrocarbon.

2. The process of claim 1 further characterized in that said reaction isterminated by treating the reaction mixture with a member of the groupconsisting of water and an aqueous alkaline solution.

3. The process of claim 1 further characterized in that said carbonylcompound and condensation product are catalytically reacted at atemperature of from about 25 to about 200 C.

4. A process for producing a synthetic resin which comprises reacting acarbonyl compound selected from the group consisting of aldehydes andketones with the condensation product of from about 5 to about 25 molsof phenol, from about 25 to about 45 mols of xylene, and from about 50to about mols of butadiene-1,3.

5. The resinous reaction product of a carbonyl compound selected fromthe group consisting of aldehydes and ketones with the condensationproduct of from about 5 to about 25 mols of a phenol having at least twonuclear hydrogen atoms, from about 25 to about 45 mols oi an aromatichydrocarbon having at least two nuclear hydrogen atoms and an alkylgroup of not more than two carbon atoms, and from about 50 to about 75mols of a conjugated aliphatic diene hydrocarbon.

6. The process defined in claim 1 further characterized in that saidcarbonyl compound is formaldehyde.

7. The process defined in claim 1 further characterized in that saidcarbonyl compound is crotonaldehyde.

8. The process defined in claim 1 further characterized in that saidcarbonyl compound is isophorone.

9. The process of claim 1 further characterized in that said carbonylcompound and said condensation product are reacted in the presence of anacidic condensation catalyst.

10. The process of claim 1 further characterized in that said carbonylcompound and said condensation product are reacted in the presence ofoxalic acid.

11. The process of claim 1 further'characterized in that said carbonylcompound and said condensation product are reacted in the presence ofhydrofluoric acid.

12. The process of claim 1 further characterized in that said carbonylcompound and said condensation product are reacted in the presence ofphosphoric acid.

13. The resinous reaction product of a carbonyl compound selected fromthe group consisting of aldehydes and ketones with the condensationproduct of from about 5 to about 25 mols of phenol, from about 25 toabout 45 mols of xylene, and from about 50 to 75 mols of butadiene-1,3.

HERMAN S. BLOCH.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,154,192 Zinke Apr. 11, 1939 2,343,845 Powers Mar. 7, 19442,378,436 Rummelsburg June 19, 1945 2,471,453 Rummelsburg May 31, 19492,558,812 Bloch July 3, 1951

1. A PROCESS FOR PRODUCING A SYNTHETIC RESIN WHICH COMPRISES REACTING ACARBONYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES ANDKETONES WITH THE CONDENSATION PRODUCT OF FROM ABOUT 5 TO ABOUT 20 MOLSOF A PHENOL HAVING AT LEAST TWO NUCLEAR HYDROGEN ATOMS, FROM ABOUT 25 TOABOUT 45 MOLS OF AN AROMATIC HYDROCARBON HAVING AT LEAST TWO NUCLEARHYDROGEN ATOMS AND AN ALKYL GROUP OF NOT MORE THAN TWO CARBON ATOMS, ANDFROM ABOUT 50 TO ABOUT 75 MOLS OF A CONJUGATED ALIPHATIC DIENEHYDROCARBON.